Photochemical properties of a Re(I) polymer containing dppz in its structure : An interplay between dark and bright states of dppz
A new polymer, P4VP-Re(dppz), based on the poly-4-vinylpyridine structure containing Re(CO)<sub>3</sub>(dppz)⁺ pendants was synthesized. Multiple morphologies of P4VP-Re(dppz), such as vesicles, spherical nanoaggregates, large vesicle compounds, rings and pyramidal structures were observ...
| Authors: | , , , , , , |
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| Format: | article |
| Status: | Published version |
| Publication Date: | 2018 |
| Country: | Argentina |
| Institution: | Universidad Nacional de La Plata |
| Repository: | SEDICI (UNLP) |
| Language: | English |
| OAI Identifier: | oai:sedici.unlp.edu.ar:10915/105765 |
| Online Access: | http://sedici.unlp.edu.ar/handle/10915/105765 |
| Access Level: | Open access |
| Keyword: | Ciencias Exactas TD-DFT AFM TEM Rhenium complexes Photochemistry Morphology |
| Summary: | A new polymer, P4VP-Re(dppz), based on the poly-4-vinylpyridine structure containing Re(CO)<sub>3</sub>(dppz)⁺ pendants was synthesized. Multiple morphologies of P4VP-Re(dppz), such as vesicles, spherical nanoaggregates, large vesicle compounds, rings and pyramidal structures were observed by AFM and TEM in cast films of P4VP-Re(dppz) in solvents of different polarity and solvent/acid mixtures. Several conformations of a model monomer of P4VP-Re(dppz) were studied by TD-DFT to ascertain the effect of protonation over the molecular structure as well as over the absorption spectroscopy of P4VP-Re(dppz). P4VP-Re(dppz) excited states and their redox reactivity towards the sacrificial reductant TEOA were studied by flash photolysis experiments either in DMF and in DMF/HClO<sub>4</sub>. Those experiments were compared to the ones derived from thermal reactions of P4VP-Re(dppz) with solvated electrons in pulse radiolysis experiments. All the photophysical and photochemical properties studied were rationalized in terms of an interplay between <sup>3</sup>IL(ππ*), <sup>3</sup>MLCT(phz) and the 3MLCT(phen) states. |
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